, Volume 26, Issue 6, pp 3671–3684 | Cite as

Highly carboxylated and crystalline cellulose nanocrystals from jute fiber by facile ammonium persulfate oxidation

  • M. Mahbubul Bashar
  • Huie Zhu
  • Shunsuke Yamamoto
  • Masaya MitsuishiEmail author
Original Research


This report describes the synthesis of highly carboxylated cellulose nanocrystals (CNCs) from jute fiber by facile oxidation with ammonium persulfate (APS). The oxidation time effects on microstructure, surface chemistry, crystal structure, and thermal properties were investigated. Crystal-like morphology was obtained with 5.2 nm average particle diameter and 300–500 nm length, depending on the oxidation time. The degree of oxidation (DO) was found to be 0.27: the highest among APS-oxidized CNCs. The carboxylic group amount of 1550 mmol kg−1 was achieved for 16 h oxidation treatment, resulting in high surface charge with the absolute zeta potential value of 40 mV. The DO value was well correlated with the peak intensity of carbonyl group ascertained from FT-IR studies: 0.12 + 0.38(I1730/I1060). As-prepared CNCs showed improved dispersibility in organic solvents up to 15 h. The APS oxidized CNCs showed good thermal stability: the onset decomposition temperature was 240 °C. Using X-ray diffraction method the crystalline index was ascertained as more than 67%. Surface modification of APS-oxidized cellulose nanofibers (CNFs) was confirmed using FT-IR and XPS. Modified CNFs were dispersed in organic solvents such as toluene and THF. Jute is a good candidate material for obtaining highly pure and crystalline CNCs through APS oxidation, exhibiting great potential as a functional material for use in diverse fields.

Graphical abstract


Cellulose nanocrystal Jute fiber Oxidation Surface modification 



This work was supported by a Grant-in-Aid for Scientific Research (B) (16H04197) from the Japan Society for the Promotion of Science (JSPS). The work was also supported by the Research Program of “Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials” in “Network Joint Research Center for Materials and Devices”. The Central Analytical Facility of IMRAM is also gratefully acknowledged for providing AFM, XPS and SEM instruments. HZ thanks the Kurita Water and Environment Foundation (KWEF) for financial support.

Supplementary material

10570_2019_2363_MOESM1_ESM.docx (621 kb)
Supplementary material 1 (DOCX 620 kb)


  1. Abraham E, Deepa B, Pothan LA, Jacob M, Thomas S, Cvelbar U, Anandjiwala R (2011) Extraction of nanocellulose fibrils from lignocellulosic fibres: a novel approach. Carbohydr Polym 86(4):1468–1475Google Scholar
  2. Abraham E, Nevo Y, Slattegard R, Attias N, Sharon S, Lapidot S, Shoseyov O (2016) Highly hydrophobic thermally stable liquid crystalline cellulosic nanomaterials. ACS Sustain Chem Eng 4(3):1338–1346Google Scholar
  3. Ahmed AS, Islam MS, Hassan A, Mohamad HaafizKh MK, Islam KN, Arjmandi R (2014) Impact of succinic anhydride on the properties of jute fiber/polypropylene biocomposites. Fibers Polym 15:307–314Google Scholar
  4. Bashar MM, Siddiquee MAB, Khan MA (2015) Preparation of cotton knitted fabric by gamma radiation: a new approach. Carbohydr Polym 120:92–101Google Scholar
  5. Bashar MM, Zhu H, Yamamoto S, Mitsuishi M (2017) Superhydrophobic surfaces with fluorinated cellulose nanofiber assemblies for oil–water separation. RSC Adv 7(59):37168–37174Google Scholar
  6. Beck-Candanedo S, Roman M, Gray DG (2005) Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions. Biomacromol 6(2):1048–1054Google Scholar
  7. Braun B, Dorgan JR (2009) Single-step method for the isolation and surface functionalization of cellulosic nanowhiskers. Biomacromol 10(2):334–341Google Scholar
  8. Bulut Y, Aksit A (2013) A comparative study on chemical treatment of jute fiber: potassium dichromate, potassium permanganate and sodium perborate trihydrate. Cellulose 20(6):3155–3164Google Scholar
  9. Camarero Espinosa S, Kuhnt T, Foster EJ, Weder C (2013) Isolation of thermally stable cellulose nanocrystals by phosphoric acid hydrolysis. Biomacromol 14(4):1223–1230Google Scholar
  10. Cao X, Ding B, Yu J, Al-Deyab SS (2012) Cellulose nanowhiskers extracted from TEMPO-oxidized jute fibers. Carbohydr Polym 90(2):1075–1080Google Scholar
  11. Chen L, Zhu JY, Baez C, Kitin P, Elder T (2016) Highly thermal-stable and functional cellulose nanocrystals and nanofibrils produced using fully recyclable organic acids. Green Chem 18(13):3835–3843Google Scholar
  12. Cheng M, Qin Z, Liu Y, Qin Y, Li T, Chen L, Zhu M (2014) Efficient extraction of carboxylated spherical cellulose nanocrystals with narrow distribution through hydrolysis of lyocell fibers by using ammonium persulfate as an oxidant. J Mater Chem A 2(1):251–258Google Scholar
  13. Dagnon KL, Way AE, Carson SO, Silva J, Maia J, Rowan SJ (2013) Controlling the rate of water-induced switching in mechanically dynamic cellulose nanocrystal composites. Macromolecules 46(20):8203–8212Google Scholar
  14. Demirbaş A (2001) Biomass resource facilities and biomass conversion processing for fuels and chemicals. Energy Convers Manag 42(11):1357–1378Google Scholar
  15. Eichhorn SJ, Dufresne A, Aranguren M, Marcovich NE, Capadona JR, Rowan SJ, Weder C, Thielemans W, Roman M, Renneckar S, Gindl W, Veigel S, Keckes J, Yano H, Abe K, Nogi M, Nakagaito AN, Mangalam A, Simonsen J, Benight AS, Bismarck A, Berglund LA, Peijs T (2010) Review: current international research into cellulose nanofibres and nanocomposites. J Mater Sci 45(1):1–33Google Scholar
  16. Espino-Pérez E, Domenek S, Belgacem N, Sillard C, Bras J (2014) Green process for chemical functionalization of nanocellulose with carboxylic acids. Biomacromol 15(12):4551–4560Google Scholar
  17. Fox JD, Capadona JR, Marasco PD, Rowan SJ (2013) Bioinspired water-enhanced mechanical gradient nanocomposite films that mimic the architecture and properties of the squid beak. J Am Chem Soc 135(13):5167–5174Google Scholar
  18. French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21(2):885–896Google Scholar
  19. Fukuzumi H, Saito T, Okita Y, Isogai A (2010) Thermal stabilization of TEMPO-oxidized cellulose. Polym Degrad Stab 95(9):1502–1508Google Scholar
  20. Fumagalli M, Ouhab D, Boisseau SM, Heux L (2013) Versatile gas-phase reactions for surface to bulk esterification of cellulose microfibrils aerogels. Biomacromol 14(9):3246–3255Google Scholar
  21. Girouard NM, Xu S, Schueneman GT, Shofner ML, Meredith JC (2016) Site-selective modification of cellulose nanocrystals with isophorone diisocyanate and formation of polyurethane-CNC composites. ACS Appl Mater Interfaces 8(2):1458–1467Google Scholar
  22. Habibi Y, Chanzy H, Vignon MR (2006) TEMPO-mediated surface oxidation of cellulose whiskers. Cellulose 13(6):679–687Google Scholar
  23. Habibi Y, Lucia LA, Rojas OJ (2010) Cellulose nanocrystals: chemistry, self-assembly, and applications. Chem Rev 110(6):3479–3500Google Scholar
  24. Hu Y, Tang L, Lu Q, Wang S, Chen X, Huang B (2014) Preparation of cellulose nanocrystals and carboxylated cellulose nanocrystals from borer powder of bamboo. Cellulose 21(3):1611–1618Google Scholar
  25. Hu Z, Berry RM, Pelton R, Cranston ED (2017) One-pot water-based hydrophobic surface modification of cellulose nanocrystals using plant polyphenols. ACS Sustain Chem Eng 5(6):5018–5026Google Scholar
  26. Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3(1):71–85Google Scholar
  27. Jahan MS, Saeed A, He Z, Ni Y (2011) Jute as raw material for the preparation of microcrystalline cellulose. Cellulose 18(2):451–459Google Scholar
  28. Jiang H, Wu Y, Han B, Zhang Y (2017) Effect of oxidation time on the properties of cellulose nanocrystals from hybrid poplar residues using the ammonium persulfate. Carbohydr Polym 174:291–298Google Scholar
  29. Lavoine N, Bras J, Saito T, Isogai A (2016) Improvement of the thermal stability of TEMPO-oxidized cellulose nanofibrils by heat-induced conversion of ionic bonds to amide bonds. Macromol Rapid Commun 37(13):1033–1039Google Scholar
  30. Leung ACW, Hrapovic S, Lam E, Liu Y, Male KB, Mahmoud KA, Luong JHT (2011) Characteristics and properties of carboxylated cellulose nanocrystals prepared from a novel one-step procedure. Small 7(3):302–305Google Scholar
  31. Leung ACW, Lam E, Chong J, Hrapovic S, Luong JHT (2013) Reinforced plastics and aerogels by nanocrystalline cellulose. J Nanopart Res 15:1636Google Scholar
  32. Lin N, Dufresne A (2013) Physical and/or chemical compatibilization of extruded cellulose nanocrystal reinforced polystyrene nanocomposites. Macromolecules 46(14):5570–5583Google Scholar
  33. Lin YC, Cho J, Tompsett GA, Westmoreland PR, Huber GW (2009) Kinetics and mechanism of cellulose pyrolysis. J Phys Chem C 113(46):20097–20107Google Scholar
  34. Lin N, Bruzzese C, Dufresne A (2012) TEMPO-oxidized nanocellulose participating as crosslinking aid for alginate-based sponges. ACS Appl Mater Interfaces 4(9):4948–4959Google Scholar
  35. Liu Z, Fatehi P, Sadeghi S, Ni Y (2011) Application of hemicelluloses precipitated via ethanol treatment of pre-hydrolysis liquor in high-yield pulp. Bioresour Technol 102(20):9613–9616Google Scholar
  36. Lu Q, Cai Z, Lin F, Tang L, Wang S, Huang B (2016) Extraction of cellulose nanocrystals with a high yield of 88% by simultaneous mechanochemical activation and phosphotungstic acid hydrolysis. ACS Sustain Chem Eng 4(4):2165–2172Google Scholar
  37. Montanari S, Roumani M, Heux L, Vignon MR (2005) Topochemistry of carboxylated cellulose nanocrystals resulting from TEMPO-mediated oxidation. Macromolecules 38(5):1665–1671Google Scholar
  38. Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40(7):3941–3994Google Scholar
  39. Mwaikambo LY, Ansell MP (2002) Chemical modification of hemp, sisal, jute, and kapok fibers by alkalization. J Appl Polym Sci 84(12):2222–2234Google Scholar
  40. Okita Y, Fujiwara S, Saito T, Isogai A (2011) TEMPO-oxidized cellulose nanofibrils dispersed in organic solvents. Biomacromol 12(2):518–522Google Scholar
  41. Oksman K, Etang JA, Mathew AP, Jonoobi M (2011) Cellulose nanowhiskers separated from a bio-residue from wood bioethanol production. Biomass Bioenergy 35(1):146–152Google Scholar
  42. Reid MS, Villalobos M, Cranston ED (2017) Benchmarking cellulose nanocrystals: from the laboratory to industrial production. Langmuir 33(7):1583–1598Google Scholar
  43. Revol JF, Bradford H, Giasson J, Marchessault RH, Gray DG (1992) Helicoidal self-ordering of cellulose microfibrils in aqueous suspension. Int J Biol Macromol 14(3):170–172Google Scholar
  44. Roman M, Winter WT (2004) Effect of sulfate groups from sulfuric acid hydrolysis on the thermal degradation behavior of bacterial cellulose. Biomacromol 5(5):1671–1677Google Scholar
  45. Saito T, Nishiyama Y, Putaux JL, Vignon M, Isogai A (2006) Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose. Biomacromol 7(6):1687–1691Google Scholar
  46. Salajková M, Berglund LA, Zhou Q (2012) Hydrophobic cellulose nanocrystals modified with quaternary ammonium salts. J Mater Chem 22(37):19798–19805Google Scholar
  47. Sehaqui H, Kulasinski K, Pfenninger N, Zimmermann T, Tingaut P (2016) Highly carboxylated cellulose nanofibers via succinic anhydride esterification of wheat fibers and facile mechanical disintegration. Biomacromol 18(1):242–248Google Scholar
  48. Soni B, Hassan EB, Mahmoud B (2015) Chemical isolation and characterization of different cellulose nanofibers from cotton stalks. Carbohydr Polym 134:581–589Google Scholar
  49. Spinella S, Maiorana A, Qian Q, Dawson NJ, Hepworth V, McCallum SA, Ganesh M, Singer KD, Gross RA (2016) Concurrent cellulose hydrolysis and esterification to prepare a surface-modified cellulose nanocrystal decorated with carboxylic acid moieties. ACS Sustain Chem Eng 4(3):1538–1550Google Scholar
  50. Sun B, Hou Q, Liu Z, Ni Y (2015) Sodium periodate oxidation of cellulose nanocrystal and its application as a paper wet strength additive. Cellulose 22(2):1135–1146Google Scholar
  51. Thomas MG, Abraham E, Jyotishkumar P, Maria HJ, Pothen LA, Thomas S (2015) Nanocelluloses from jute fibers and their nanocomposites with natural rubber: preparation and characterization. Int J Biol Macromol 81:768–777Google Scholar
  52. Tian C, Fu S, Habibi Y, Lucia LA (2014) Polymerization topochemistry of cellulose nanocrystals: a function of surface dehydration control. Langmuir 30(48):14670–14679Google Scholar
  53. Wang H, Huang L, Lu Y (2009) Preparation and characterization of micro-and nano-fibrils from jute. Fibers Polym 10(4):442–445Google Scholar
  54. Way AE, Hsu L, Shanmuganathan K, Weder C, Rowan SJ (2012) pH-responsive cellulose nanocrystal gels and nanocomposites. ACS Macro Lett 1(8):1001–1006Google Scholar
  55. Yang H, Yan R, Chen H, Lee DH, Zheng C (2007) Characteristics of hemicellulose, cellulose and lignin pyrolysis. Fuel 86(12–13):1781–1788Google Scholar
  56. Yu H, Qin Z, Liang B, Liu N, Zhou Z, Chen L (2013) Facile extraction of thermally stable cellulose nanocrystals with a high yield of 93% through hydrochloric acid hydrolysis under hydrothermal conditions. J Mater Chem A 1(12):3938–3944Google Scholar
  57. Yu HY, Zhang DZ, Lu FF, Yao J (2016) New approach for single-step extraction of carboxylated cellulose nanocrystals for their use as adsorbents and flocculants. ACS Sustain Chem Eng 4(5):2632–2643Google Scholar
  58. Zhang Y, Karimkhani V, Makowski BT, Samaranayake G, Rowan SJ (2017) Nanoemulsions and nanolatexes stabilized by hydrophobically functionalized cellulose nanocrystals. Macromolecules 50(16):6032–6042Google Scholar
  59. Zhu H, Fang Z, Preston C, Li Y, Hu L (2014) Transparent paper: fabrications, properties, and device applications. Energy Environ Sci 7(1):269–287Google Scholar
  60. Zhu H, Luo W, Ciesielski PN, Fang Z, Zhu JY, Henriksson G, Himmel ME, Hu L (2016) Wood-derived materials for green electronics, biological devices, and energy applications. Chem Rev 116(16):9305–9374Google Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Institute of Multidisciplinary Research for Advanced Materials (IMRAM)Tohoku UniversitySendaiJapan
  2. 2.Department of Textile EngineeringMawlana Bhashani Science and Technology UniversitySantosh, TangailBangladesh

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